Azo dyes derived from 4-amino benzothiazole-or benzothiadiazole groups



Unite States Patent 3,388,114 AZO DYES DERIVED FROM 4 AMINO BENZOTHEAZOLE- OR BENZOTHHADI- AZOLE GROUPS Shinya Ito, Kyoto, Katsuo Kanno, Ohtsu-shi, and Ryoichi Nalragawa, Fuse-shi, Osaka-flu, Japan, assignors to Daito Chemical industry (10., Ltd, Osaka, Japan No Drawing. Filed Euly 15, 1965, Ser. No. 472,339 Claims priority, application Japan, July 20, 1964, 39/4ll,374, 39/ 10,375 6 Claims. (Cl. 266-157) ABSTRACT OF THE DlStZLOSURE Water-insoluble monoazo dyestufis of the formula wherein is a member selected from the group consisting of the residues of benzothiazol, 1,2,3-benzothiadiazole and 2,1, 3-benzothiadiazole, said residues being substitutable with halogen, alkyl, alkoxy, acyl, alkylamino, dialkylarnino, acylamino and mercapto; and A is a member selected rom the class consisting of aromatic rings, heterocyclic, cycloaliphatic and aliphatic groups, a hydroxyl group being attached thereto at one of the ortho positions with respect to the position of attachment of said A to the -N=N group and the other positions of said A being substitutable with hydrogen, halogen, hydroxy, alkoxy, alkylamino, dialkylarnino, arylarnino, phenyl, substituted phenyl, carboxylic esters, carboxylic amides and heterocyclic group are used with particular effectiveness in the dyeing of metal compound-containing polyolefinic shaped articles.

This invention relates to new water-insoluble monoazo dyestuffs which are useful to impart bright and fast colors to polyolefin articles containing a metal compound.

In general, the resins predominantly of polyolefins such as polypropylene and polyethylene do not essentially possess dyeability. Although numerous attempts have been made to improve their dyeability by introduction of sites receptive to dyes, the colorfastness to the various agents which cause fading was not satisfactory and hence it was not possible to obtain dyed articles thereof which were serviceable. Lately, much research is being conducted into a method of dyeing wherein the polyolefin is incorporated with a metal compound and then it is dyed with a dyestuff containing a slightly ionizable acid group or a similar group. Dyestuffs which are used for such metal-containing polyolefins are disclosed in the American Dyestuff Reporter (1963), pages 31 and 527, Japanese patent application publication No. 4,477/ 1963, and Belgian patents specification Nos. 632,652 and 632,653. As dyestuffs which form coordinate bonds with metals, the water-soluble dyes having a salicylic acid residue and o-hydroxyazo residue in the direct dyes and acid dyes have already been known for a long time. Further, recently there is available the 1:2 type complex azo dyestuff, the so-called formazan type dyestuif, not containing a water-soluble group, which are for wool and polyarnide use. However, even though attempts have been made to impart coloring directly to the foregoing metal- 3,388,114 Patented June 11, 1968 "ice containing polyolefin shaped articles with the non-metallized dye nucleus of these dyestuffs, a serviceable coloring cannot be imparted at all. On the other hand, the compounds mentioned in the foregoing American Dyestuff Reporter, such as alizarin-1,8-dihydroxyanthraquinone, 1,8-dihydroxynaphthalene and o-carboxyl-o'-hydroxyazobenzene, which are believed to be metallizable in all cases are weak as to their ability to bond with metals. Hence, although some may be able to impart a pale coloring, they are still unsatisfactory with respect to their fastness.

Again, although dyed articles having a deepness of shade and fastness to a certain extent can be obtained in the case of some of the compounds disclosed in Japanese patent application publication No. 4,477/ 1963, for example, the derivatives of 5-arylazo-8-hydroxyquinoline, 7-hydroxy-4-arylazo indazole, 7-arylazo-4-hydroxybenzothiazole, by limiting the substituent to the aryl group, the classes of hues obtainable are limited to within a narrow range. Again, among the o,o'-dihydroxyazo derivatives disclosed in Belgian patent specification No. 632,652, those whose structure is limited can achieve in part the imparting of coloring as intended. The dyeing power is low however and the matter of selectivity is involved depending upon the class of metal.

On the other hand, the azo dyestuff derivatives containing thiazole or oxazole, as disclosed in Belgian patent specification No. 632,653 are believed to be the best dyestuffs that are of pratcical use at the present time in that they possess fastness properties to the various agents which cause fading and in that deep shades are obtainable. However, the dyestulf of this structure also is deficient as far as level dyeing is concerned on account of the fact that its speed of adherence is fast. In addition, bright colors cannot be obtained because of the dullness of its hues.

Hence, as hereinabove indicated, numerous problems needing further research still remain in the case of the conventional metal-containing dyestuffs for polyolefin use, including not only such matters as dyeing power and fa-stness to the various agents which cause fading but also such matters as level dyeing, hue and brightness of color. Although there are many elements and groups that are generally known to be capable of forming a coordinate bond and some proposals have been made as to compounds that are metallizable, it is a ditficult feat to solve this matter merely by analogical inference from general theories. Great inventive ability is required to solve these problems and find a dyestuff of value.

An object of the present invention is to provide new water-insoluble monoazo dyestuffs which can be used with particular effectiveness in dyeing metal compounding-containing polyolefinic shaped articles, which moreover are available in hues covering a very broad range, and which dye the metal compound-containing polyolefinic shaped articles to a bright color tone, as contrasted with the dull color tone characteristic of the conventional metal complex dyestuffs, and in which the coloring imparted possesses superior fastness to light, dry cleaning, Washing, rubbing and sublimation. Other objects and advantages of the present invention will be apparent from the following description.

The dyestuffs according to the invention are waterinsoluble monoazo dyes having the formula wherein is a member selected from the group consisting of the residues of benzothiazole, 1,2,3-benzothiadiazole and 2,1,3-benzothiadiazole, said residues being substitutable with halogen, alkyl, alkoxy, acyl, alkylamino, dialkylamino, acylamino and mercapto; and A is a member selected from the class consisting of aromatic rings, heterocyclic, cycloaliphatic and aliphatic groups, a hydroxyl group being attached thereto at one of the ortho positions with respect to the position of attachment of said A to the N=N- group and the other positions of said A being substitutable with hydrogen, halogen, hydroxy, alkoxy, alkylarnino, dialkylamino, arylamino, phenyl, substituted phenyl, carboxylic esters, carboxylic amides and heterocyclic group.

As can be seen in the foregoing formula, the dyestuff of the present invention is composed of a coupling component A and a diazo component having the structure wherein a benzene ring and a hetero ring containing at least one tertiary nitrogen atom have been condensed. Further, said tertiary nitrogen atom is directly attached to the benzene ring to a carbon atom at the ortho position with respect to the carbon atom which bonds with the diazo group, -N=N. While the diazo component can have a non-solubilizing substituent, as hereinbefore indicated, it does not contain a soluble group such as a carboxylic acid group or a sulfonic acid group.

The coupling component is either an aromatic, heterocyclic, aliphatic or cycloaliphatic compound which has a hydroxyl group which can assume the ortho position with respect to the azo group. The positions other than at which said hydroxyl group is attached can be substituted with the various substituents that have been hereinbefore mentioned.

As the coupling component there are included, e.g., fi-naphthol, p-cresol, p-chlorophenol, p-bromophenol, 3, 4-dimethylphenol, 3-dimethylamino-phenol, 3-diethylamino-phenol, hydroquinone monomethyl ether, 6-chloro-2- naphthol, 2-hydroxy-3-naphthoic acid ethyl ester, 6- methyl-Z-naphthol, 4-methoxy-1-naphthol, 4-chloro-1- naphthol, 4-methyl-1-naphthol, l-phenyl-S-methyl-S-pyrazolone, l-(o-chlorophenyl)-3-rnethyl-5-pyrazolone, 1- (o-methyl-phenyl)-3-methyl-5-pyrazolone, 3 methyl-5- pyrazolone, 3-hydroxy-S-methylthionaphthene, resorcinol, acetoacetic ethyl ester, acetoacetic anilide, acetoacetic ethyl amide, dimedone and acetylacetone; and derivatives thereof.

The invention monoazo dyestuffs can be prepared by diazotizing the foregoing amines in customary manner and thereafter coupling the diazotized amines with the foregoing coupling components under either alkaline or acid conditions.

The method of dyeing shaped articles of polyolefin polymers according to the present invention comprises dyeing a shaped article of polyolefin polymer obtained by melt shaping polyolefin resins wherein is incorporated at least 0.01% by weight, based on the resin, of a transition metal compound, calculated as the metal, with a waterinsoluble monoazo dyestufi of the formula wherein and A have the precedingly recited siguificances.

The polyolefin resins which are used in this invention include the homopolymers of wolefins, such as ethylene, propylene, 3-methylbutene-1, 4-methylpentene-1 and 5- methylhexene-l. Also included are the copolymers of two or more of these a-Ol6fi11S as well as the graft polymers consisting of these parent polymers to which other monomers have been grafted. Other polymers, for ex,- ample, polyesters, polyamides, polyureas, polyurethanes, epoxy resins or polycarbonates may be mixed with the foregoing olefin polymers. Further, they may also contain antioxidants of the phenol or amine type, ultraviolet absorbers or optical brightening agents such as benzophenone or triazine derivatives, delustrants such as titanium dioxide, stabilizers or dyeing power promoters such as the alkaline earth metal salts of aliphatic acids or organic phosphates, or plasticizers such as dioctyl phthalate.

The metal compounds to be incorporated in the polyolefin polymers in accordance with the invention dyeing method are the dissociable compounds of transition metals. The preferred transition metals include nickel, zinc, copper, chromium and cobalt, of which nickel is to be particularly preferred. As the dissociable compounds of the transition metals, the use of the organic acid salts and the organic complexes is preferred. Particularly preferred are the higher car-boxylic acid salts such as nickel.

stearate, nickel palmitate, nickel oleate, nickel naphthenate, chromium stearate, cobalt stcarate and copper naphthenate. Conjointly with these higher carboxylic acids or in their stead can also be used the salts of amino acids such as the nickel salt of Ot-fll'l'lll'lO acid, alkyl phosphates such as di-n-propyl nickel phosphate and n-hexyl ethyl nickel phosphate, suifonates such as dodecyl benzene nickel sulfonate and t-octyl benzene chromium sulfonate, as well as the benzoates, salicyliates, alkyl phosphites; naphthionates and alkyl sulfates. In addition, the organic complexes such as nickel acetylacetonate and zinc-Shydroxyquinolinate, and the weak chelate compounds such as the metal chelate compounds of the acetoacetic acid derivatives and malonic ester derivatives are also usable. The dyeing speed is relatively slow in the case of the metal chelate compounds however, since the substitution of chelate takes place between the chelate compounds and the dyestuff.

The polyolefin resin, before its melt-shaping, is incorporated with at least 0.01% by weight, and preferably O.1-l% by weight, based on the resin, of a transition metal compound, calculated as the metal.

Although the metal compounds of copper, silver and gold, which are incorporated in the polyolefin compounds according to the present invention, form a satisfactory coordinate bond with the dyestuffs of the invention, they have the drawback that they readily change to brown in the polyolefin resin when the melting temperature is high. On the other hand, when the metal compounds of zinc, cadmium, mercury, titanium, zirconium and hafnium are used, little, if any, discoloration takes place during meltshaping of the polyolefin resins, though slight decomposition of the metal compounds is noted. Their property of forming coordinate bonds with the invention dyestuff is slightly inferior, however. In the case of the metal compounds of chromium, molybdenum and tungsten, they are stable in the molten polymer and no thermal discoloration takes place. Although their dyeing etfectives resulting from their coordinate bond with the invention dyestutf is somewhat inferior, their colorfastness to the various agents which cause fad'mg is satisfactory. The metal compounds of iron, cobalt and nickel are satisfactory with respect to their thermal stability in the molten polymer as well as in their property of forming a coordinate bond with the dyestuffs of this invention and in their fastness properties. The use of a cobalt compound involves some deterioration of the weatherability of the polymer, however.

When the hues and brightness that are obtainable by means of the dyestufis as used in this invention and the fastness properties of the resulting dye product are considered, nickel, zinc, copper and chromium are desirable as the metal component, nickel and Zinc being particularly preferred.

In dyeing in accordance with the present invention the foregoing meal compound-containing polyolefin shaped articles, these various new monoazo dyes, as hereinbefore described, are kneaded together with an anionic or nonionic dispersant and/or a solubilizing agent and rendered into finely divided particles. Or, if necessary, an inorganic salt such as sodium chloride is added and the mixture is made into an aqueous paste or is, after drying, ground into a finely divided powder by means of an ultra high speed pulverizer. As the dispersant or solubilizing agent, there are used the anionic or nonionic activators, which are optionally chosen. However, when this dyestuff is used dissolved in a polyoxyethylene nonionic surfactant wherein the polyoxyethylene content is 60-85%, instead of the ordinary anionic levelling agent, this dyestuif permeates to the interior of polyolefin shaped article homogeneously and thoroughly. Hence, it is particularly desirable to prepare the dyeing liquid using this type of dyestuif treating agent. A particularly good dyeing liquid can be obtained by melt blending this type of dyestutf treating agent with the dye and thereafter diluting with water.

In this invention, optionally chosen dyeing methods, such as the carrier method, the solubilization method, the high temperature-high pressure method and the thermosol method, can be employed in carrying out the dyeing by using the aforementioned specific dyestuffs. The amount used of the dyestuff can be varied over a broad range, but an amount about (Ll-6.0%, based on the article to be dyed, is suitable. The dyeing temperature should preferably range between 70 and 120 C., there being a tendency to a decrease in the rate of adsorption at temperatures higher than this.

While excellent dyeing effects are had When the dyeing liquid is adjusted to a pH 3-8 in the invention dyeing method, a dyeing liquid which is strongly acid or above a pH 9 results in a slight decrease in the color values obtained.

The dyed article, after washing with water, is treated with a Wash liquid in which is incorporated soap or an equally effective surfactant, followed by water washing and drying. Alternatively, reduction washing may be carried out using hydrosulfite, caustic soda and a suitable surfactant.

According to the present invention, dyed articles of remarkable brightness can be obtained, which are free of the dullness which was characteristic of the articles dyed with the conventional metal complex dyestuffs. It is also possible to obtain dyed products which excel in fastness to sunlight, washing, dry cleaning, rubbing and sublimation.

The dyestuffs according to the invention also exhibit an ideal dyeing speed curve, and remarkably satisfactory levelness of dyeing can be obtained. In addition, as these dyestuffs render the molecular volume great in the polyolefin shaped articles by the formation of metal complexes therein, their solubility in water or solvents is greatly reduced, with the consequence that there is the effect that the transfer, detachment, extraction or sublimation of the dyestuff from the polymer substrate is completely prevented.

The following examples are given for illustrating the present invention. The evaluation of the fastness properties were in accordance with the following AATCC methods.

Fastness to light (AATCC 16A-l963) Fastness to washing (AATCC 36 1961-01) Fastness to rubbing (AATCC 8-1961) Fastness to dry cleaning (AATCC 85-1963) Fastness to sublimation (AATCC 5-1957) 6 EXAMPLE 1 A solution of 19.4 g. of 2-methyl-4-arnino-6-meth0xybenzothiazole in 41.6 g. of 35% hydrochloric acid and 250 g. of water was cooled with ice to 0-5 C. and gradually dropped into a solution of 7.2 g. of sodium nitrite in 21.6 cc. of water, after which the solution was stirred at this temperature for 30 minutes. Then after adding 0.5 g. of decolorizing carbon, the solution was filtered.

The so prepared diazotized solution was dropped at 10-15 C. into a coupling component solution prepared by dissolving 15.1 g. of beta-naphthol in a solution consisting of 58.7 g. of 30% caustic soda in 200 cc. of water. After stirring this solution for 30 minutes at the foregoing temperature, the deposited coloring matter was filtered, followed by again suspending this coloring matter in 300 cc. of water. Then after acidifying the suspension to Congo red with dilute hydrochloric acid, it was adjusted to pH 7.5-8 with 10% ammonia water and again filtered, after which the crystals obtained were washed with water and dried at 60 C.; 30.7 g. of reddish brown crystals were obtained in this manner. These crystals were recrystallized from dioxane and reddish brown crystals of 4-(2'-hydroXy-naphthyl 1 azo)-6methoxy-2-rnethylbenzothiazole having a melting point of 195-198 C. were obtained. N analysis values: calculated 12.03%, found 12.00%.

Thirty grams of the foregoing dyestutf were thoroughly kneaded together with 45 g. of a condensation product formed from 2 mols of beta-naphthalene sulfonic acid and 1 mol of formaldehyde, 5 g. of a condensation product formed from 1 mol of nonylphenol and 10 mols of ethylene oxide neutralized with monosulfonic acid ethanolamine and 20 g. of p-toluene sodium sulfonate, in a threeroll mill using 20 g. of water. The resulting paste, after being dried at 60 C., was ground in an ultrahigh speed pulverizer to a finely divided dyestuff composition. When 0.5 g. (dyestuif content 30%) of the so obtained dyestuff composition was added to 300 cc. 40 C. water, a homogeneous dispersion was obtained. When 10 g. of filaments obtained by melt-spinning and drawing to 5 times at 240 C. in customary manner blended chips obtained by melt blending parts of isotactic polypropylene powder having an inherent viscosity of 1.53 (measured in tetralin at C.) and 5 parts of nickel stearate were dipped in this dispersion, the temperature being raised to 98 C. in 20 minutes and the treatment being carried out for one hour, followed by the customary soaping treatment, a product dyed a bright blueish red (lightness 17.4%, purity 81.0%, dominant Wave-length 499.2 m was obtained which possessed color fastness to sunlight, washing, rubbing, sublimation and dry cleaning as indicated below.

Grade Fastness to light 7 Fastness to washing 5 Fastness to rubbing 5 Fastness to sublimation 5 Fastness to dry cleaning 5 EXAMPLE 2 19.4 grams of 2-methyl-4-amino-6-methoxybenzothiazole were diazotized as in Example 1. When this diazotized product was treated as in Example 1 using 16.6 g. of 4-methoxy-1-naphthol as the coupling component, 32.1 g. of dark purple crystals were obtained. Then when these crystals were recrystallized from dioxane, dark purple crystals of 4-(1-hydroxy-4-methoxynaphthyl-2'- azo)-2-rnethyl-6-methoxybenzothiazole having a melting point of -188 C. were obtained. N analysis values: calculated 11.75%, found 11.73%. 0.2 g. of the so obtained dyestuff and 0.2 g. of a nonionic surfactant obtained from nonylphenol and 20 mols of ethylene oxide were thoroughly kneaded, after which the kneaded product was suspended in 250 cc. of water to prepare a dye oath. 10 g. of filaments obtained by spinning and drawing 7 8 to 5 times blended chips containing 97 parts of isotactic containing 5% of zinc stearate were dyed a blueish red polypropylene having an inherent viscosity of 1.60 (meashaving fastness to sunlight, Washing, rubbing, sublimaured in tetralin at 135 C.), 3 parts of nickel stearate and tion and dry cleaning. (Lightness 5.9%, purity 63.0%, 2 parts of zinc stearate were dipped in this dye bath and dominant wave-length 528.5 in treated for 1 hour at 98 C. After washing with water, 5 soaping treatment in customary manner was given the Grade dyed filaments. As a result, a product dyed a deep blue astn ss to light 5-6 (lightness 7.0%, purity 73.0%, dominant Wave-length EI S t Washing 469.0 Inn) was obtained which possessed fastness to sun- Ffl neSS t0 rubbing 5 light, Washing, rubbing, sublimation and dry cleaning as 1 stness to sublimation 5 indicated below. P21501655 dry Cleaning 5 Grade Fastness to light 7 EXAMPLE 5 Fasmess to Washing 5 A solution of 19.4 g. of 2-methyl-6-methoxy-4-amino- Fastness to rubklmg 5 19 -bei'lzothiazole diazotized as in Example 1 was added at Fastness to subhmanpn 5 10-15 C. to a coupling component solution consistin of Fastness to dry cleamng 5 17.3 g. of mdiethyl-aminophenol in 57.9 g. of glacial EXAMPLE 3 acetic acid. After adjusting this mixture to a pH 4-4.5

by adding sodium acetate, it was stirred for 5 hours. The

When 19.4 g. of 2-methyl-6-methoxy-4-aminobenzocrystals deposited, after being filtered, were again susthiazole were diazotized as in Example 1, followed by pended in 200 cc. of water and the suspension was carrying out the same treatment as in said example using acidified to Congo red. Then after adjusting the pH of 18.3 g. of 1-phenyl-3-methyl-5-pyrazo1one as the coupling the suspension to 7.5-8 with 10% ammonia water, filtracomponent, 35.8 g. of yellow crystals of 4-(1'-phenylion is again carried out, followed by washing the crystals 3-methyl-5-pyraz0lone-4'-azo)-2 methyl-G-rnethoxybenwith water and drying at 60 C. There were obtained zothiazole (dyestuif A) were obtained. Melting point 293 g. of reddish brown crystals of 4-(1'-hydroxy-5'-N,N- 226-228 C. N analysis values: calculated 18.46%, found diethylamino-phenyl 2 azo) 2 methyl 6 methoxy- 18.41%. On the other hand, by using B-methyl-S-pyr-azobenzothiazole. Melting point 113-115 C. N analysis lone instead of the 1-phenyl-3-methyl-5-pyrazolone and values: calculated 15.12%, found 15.08%. By using the carrying out the same treatment, 35.8 g. of yellow crystals so obtained dyestuff and carrying out the treatment as in of 4 (3'-rnethyl-5'-pyrazolone-4'-azo) 2 methyl-6- Example 1, polypropylene fibers containing 5% nickel methoxybenzothiazole (dyestuff B) were obtained. Meltstearate were dyed red having fastness to sunlight of ing point 174-177 C. N analysis values: calculated Grade 4-5, to drp cleaning of Grade 4, to laundering 23.09%, found 23.05%. When these dyestuffs were used of Grade 5, to rubbing of Grade 5 and to sublimation and polypropylene fibers containing 5% of zinc stearate of Grade 5. (Lightness 20.3%, purity 62.1%, dominant were treated as in Example 1, these fibers were dyed wave-length 600.5 me.) In alike manner, polypropylene a brilliant yellow having fastness to sunlight, washing, fibers containing 5% of zinc stearate were dyed a fast rubbing, sublimation and dry cleaning as tabulated below. yellowish red.

Light- Dominant Fastness grade Dyencss, Purity, wave-length, stutf percent percent m Light Wnsh- Rub- Subli- Dry ing bing mation cleaning EXAMPLE 4 EXAMPLE 6 When 19.4 g. of 2-methyl-6-rnethoxy-4-aminobenzo- 19.4 grams of 2-methyl-6-rnethoxy-4-1mino-benzothiazole were diazotized as in Example 1 and then treated thiazol Was diazotized in the same manner as in Example as in said example using 17.2 g. of 5-methyl-3-hydroxy- 1 and coupled with each of the coupling components inthionaphthene as the coupling component, 30.8 g. of dicated in the following Table I such as alkylphenols and reddish brown crystals of 4-(5-methyl-3-hydroxythio :alkoxyphenols in the same manner as in Example 1 to naphthyl-4'-azo)-2-rnethyl-6-methoxybenzothiazole were give a corresponding monoazo dyestuff. The melting obtained. Melting point 167-170" C. N analysis values: point, N analysis values, color values and fastness propcalculated 12.45%,found 12.40%. erties are shown in Table I. The color shades obtained By using the so obtained dyestulf and carrying out the by coloring polypropylene fiber withv the use of these treatment described in Example 1, polypropylene fibers dyestuffs are also shown in the same table.

TABLE 1 Corresponding Monoazo Dyestuffs Result of Dyeing Color value Fastness t0- Coupling Shade of Shade of component Meltpolypropylpolypropyl- Domi- Wnsh- Rub- Subli- Dry (Material ing Calcu- Found ene fiber ene fiber Llght- Purity naut Light ing bing mation clearing used) point, lnted containing containing ness wave- C. 5% 0i 5% of length nickel zinc stearate stearate -Methyl-phenol 179-181 13.40 13.38 Purple Purple 5.6 52.9 -554.5 4-5 5 5 5 5 2,4-dimethy1phenol 158-160 12. 83 12.79 Deep blue Deep blue 6.1 45.8 565.0 4-5 5 5 5 5 3,4-dimethylphenol- 167-168 12. 83 12. 81 Blueish red-. Blueish red-- 4-5 5 5 5 5 p-Tert-butylphenol 132-133 12.82 11.80 Red purple Red purple-.- 8.0 55.4 5-6 5 5 5 4 z-Tfirt-blutyl-i'methyl- 189-191 11.37 11.32 Reddish blue. Blueish red 5 5 5 5 4 p eno p-Methoxy-phenol 133-136 12. 76 12.70 Blue Blue 13.8 59.5 5-6 5 5 5 5 p-Ethoxy-phenol 112-115 12. 24 12.19 Lime violet do 5-6 5 5 5 5 p-Benzyloxyphenol 194-196 10.36 10.32 Blue ..do 5 5 5 5 4 2-Methoxy-4-allyl- 158-159 11.37 11.34 Slightly 5 5 5 5 5 phenol. blueish grey.

m-Hydroxydiphenol- -97 14. 35 14.29 Red Orange red. 18.0 43.0 616.0 5 5 5 5 5 9 EXAMPLE 7 Using various diazo components and coupling components, corresponding azodyestuffs of the present invention were obtained. A polypropylene fiber containing 5% of either nickel stearate or zinc stearate was colored with the use of the so obtained azo dyestuffs. The color shades are shown in Table II.

TABLE II Shade of poly- Shade of propylene fiber polypropylene Dyestufi containing nickel fiber stearate containing zinc stearate Z-methyl-fi-rnethoxy-4-(2-hydroxy- Red purple- Red purple.

5fhlorophenylazo)-benzothiazo e. z-methyl-fikmethoxy i-(2-hydroxydo Do.

5'carboxyamyl-phenyl)benzethiazole. 4-(2-hydroxy-Bearboxybutyl- Blueish red. Do.

naphthylazo)-6-methyl-benzothiazole. 2-methyl-4-(a-acetylacetic anilid- Yellow Yellow.

(a)-ylazo) -benzothiazole. 2-methyl-4-(a-acetylacetic ethyl- .do

(a)-azo)-benzothiazole. 2-rnethyl-6-methoxy-4-(2,6dl- Golden color- D o.

hydroxy-Q-dimethyldichlorohexylazo)-benzothiazole. 2methyl-6-nieth0xy-4-(a-acetyl- Yellow Greemsh yellow.

aceton-(a) -ylazo)-benzothiazole. 2-rnethy1-6-rnethoxy-4-(1,3'-iudan- Red orange. Red orange.

dion2-ylazo)-benzothiazole. 2-methyl-6-rnethoxy4-(2-hydroxy- Red purple. Red purple.

5 ,6 ,7 ,8 ,-tetrahydronaphthylazo)-benzothiazole 2,5,7-trimethyl-4-(2'-liydroxy Blue red Blue red.

naphthylazo)-beuzothiazole.

2acetylamino-6'ethoxy-4-(2'hydroxy-3 ,5 -dimethylphenylaz 'bcnzothiazole.

Reddish blue. Iteddish blue.

2-acetylamino-4-(2-hydr0xy-4di- Red Red.

ethylaminophenyl)-6-methylbenzothiazole.

4-(1-phenyl-3-methyl-5-pyrazolon- Yellow Yellow.

4-ylazo)-6-methylbenzothiazole.

4-(2-hydroxy-5-methylphenylazo)- Purple Purple.

fi-rnethylbenzothiazole.

2-rnethyl-4-(4-ethoxy-l-naphthol-Z- Blue Blue.

ylazo)-6-chlor0benzothiazole.

2-rnethyl-4-(2-hydr0xy-4-di- Orange red Orange red.

methylaminophenylazo)-6- chlorobeuzothiazole.

2-dimethylamino-4-(2-hydroxy- Red purple Red purple.

naphthylazo)-benzothiazole. 2-dimethylarnino-4-(3-methyl 5- pyirazolon-y-ylazo)-benzotlna- 2-dimethylamino-4-(5-hydroxyacenaphtheny-ylazo)-benzothiazole.

Yellow orange... Yellow orange.

Reddish blue. Reddish blue.

2-mercapto-4-(2-hydroxynaphthyl- Blue red Blue red.

azo)-6-methylbenzothiazole.

2-rnercapto4(2-hydroxy-5-tert- Red purple. Red purple.

butyl)-6-methylbenzcthiazole.

2-methyl4-(2hydroxy-3,5-di- Blue Blue.

methoxyphenylazo)-6-methoxybenzothiazole.

EXAMPLE 8 8 grams of 4-amino-6-methoxy-1,2,3-benzothiazole were dissolved in 24 g. of a 98% sulphuric acid and a solution of 3.7 g. of sodium nitrite dissolved in 37 g. of a 98% sulphuric acid at 70 C. was dropped thereinto at 8 to 10 C. After stirring for one hour at a temperature below 10 C., the obtained solution was gradually dropped at 10 to G, into a coupling component solution prepared by dissolving 5 g. of p-cresol into a solution of 165 g. of 30% caustic soda in 400 cc. of water. After stirring at this temperature for 30 minutes, the precipitated crystals were filtered and again suspended in 200 cc. of water. The suspension was acidified to Congo red with a diluted hydrochloric acid and the pH thereof was adjusted to 7.5 to 8.0 with 10% aqueous ammonia.

The suspension was then filtered, Washed and dried at 60 C. There were obtained 122 g. of brown crystals having a melting point of 184 to 187 C. Further, brown crystals of 4-(1-hydroxy4'-methyl-benzene-2-azo)-6- methoxy-l,2,3-benzothiadiazole having a melting point of 188 to 190 C. were obtained by re-crystallization from dimethylformamide. N analysis values: calculated 18.66%, found 18.65%.

30 grams of the obtained dyestuff were kneaded well with 45 g. of a condensation product prepared from 2 moles of fl-naphthalenesulphonic acid and 1 mole of formaldehyde, 5 g. of a salt of a condensation product formed from 1 mole of nonylphenol and 10 moles of ethylene oxide neutralized with monosulphonic acid ethanolamine, 20 g. of p-toluene sodium sulphonate and 20 g. of water by means of three rolls. The paste so obtained was dried at 60 C. and pulverized on a super high speed pulveriser to thereby form a dyestuif composition in the form of fine particles.

0.5 gram of the so prepared dyestulf composition (30% of pure dyestuff content) was added to 300 cc. of water at 40 C. to form a homogeneous dispersion. 10 grams of a filament which was prepared by melt spinning a chip mixture of parts of powdery isotactic polypropylene having an intrinsic viscosity of 1.53 (measured in tetralin of C.) and 5 parts of nickel stear-ate at 240 C. in accordance with customary manner and then drawing the spun filament to 5 times the original length was immersed in said dispersion and heated to 98 C. After one hours treatment, the filament was treated with soap. There Was obtained lustrous, slightly greenish blue dyeing having excellent fastness to sunlight (Grade 5-6), drycleaning (Grade 5 washing (Grade 5), rubbing (Grade 5) and sublimation (Grade 5). It had a lightness of 8.8%, purity of 44.0% and a dominant wavelength of 484.7 mg.

EXAMPLE 9 8 grams of 4-amino-6-methoxy-1,2,3-benzothiazole were diazotized in the same manner as in Example 8, and gradually dropped at 10 to 15 C. into a coupling component solution prepared by dissolving 4.5 g. of 3- methyl-S-pyrazolone into a solution consisting of g. of 30% caustic soda and 400 cc. of water. After stirring for 30 minutes at this temperature, the precipitated crystals were filtered and again suspended in 200 cc. of water. After the same treatment as in Example 8, there were obtained 11.8 g. of yellow brown crystals having a melting point of 182 to 186 C. Brown crystals of 4-(3- methyl-5'-pyrazolone-4'-ylazo)-6-methoxy-1,2,3 benzothiazole having a melting point of 193 to 195 C. were obtained by re-crystallization from dimethylformamide. N analysis values: calculated 28.95%, found 28.91%.

The so prepared dyestuff colours a polypropylene fiber containing 5% of nickel stearate in yellow orange colour. The dyeing had an excellent fastness to sunlight (Grade 5-6), washing (Grade 5 rubbing (Grade 5), sublimation (Grade 5) and drycleaning (Grade 5) and also a lightness of 40.0%, a purity of 87.5% and a dominant wavelength of 588.0 mm.

EXAMPLE l0 8 grams of 4-amino-6-methoxy-1,2,3-benzothiazole were diazotized in the same manner as in Example 8. The diazotized product was coupled with each of the coupling components listed in Table 111 such as alkylphenols, alkoxynaphthols and alkoxyphenols in the same manner as in Example 8 to form a corresponding monoazo dyestuff.

The melting point of said dyestuff and the results of the coloring of a polypropylene fiber by means of each of these dyestuffs are shown in the table.

TABLE III Shade of poly- Shade of poly- Color values Fastness to Melting propylene fiber propylene fiber point of containing 5% containing 5% Domi- Used Material dyestuti, of nickel stearate of zinc stearate Lig it- Purity, nant Wmh- Rub- Subli- Dry- C. ness, percent wave- Light ing bing mation cleanpercent ngtn, ing

N, N-dieti l-m-aininopheuol.. 263-264 Purple .eddish purple-- 9.6 48.0 567.() 4-5 5 5 5 5 4-mcti1oxy-1-naputiiol 224 328 Blueisn green..- Blueisn green-.. 23.6 420 485.7 4-5 5 5 5 5 tallyl-ZanetnoxyplieuoL- 185.5-187 Green Greei1...... 11.5 21.0 499.8 4-5 5 4 4 5 p-C.aloropne=.iol R O-191.5 Brilliant blue-.. Brig it b1ue-- 4.6 19.8 423.5 4-5 5 4 4 4 p-Tert-butylphenol- 163-165 Blu 4.3 20.1 471.6 5-6 5 5 5 5 2, 4-(linietnyl-plienoL 162-165 9.6 20.5 490.8 5-6 5 5 5 5 p-lletlioxy-phenol 177-179 Blueish grceu .do 13.7 20.5 499.5 5-6 5 5 5 5 EXAMPLE 11 TABLE IVContinued Each of the nionoazo dyestuffs indicated in Table IV Dyestufi i f was prepared by coupling 4-arnino-1,2,3-benzotl1iadiazole I v l derivative with a coupling component. Using this dyestufi 5 g gfgfi g gg g gg gg Purple Purple a 01 ro lene fiber containing 5% of either nickel s-meni iae nyamxy-s' riieth i- Blue Blue P YP Py 1 1} stearate (A) or zinc stearate (B) was colored. The shades ififl mo H are also shown in the table. -inetliyl-4-(2hydrexy-5-etlioxy- Green blue Green blue.

pielylflzo)'bQlIZOiZilifldiflZOlG' 1;, S-niethoxyA-(2-liydroxy-1-naph- Red blue Do. TABLE Iv 5 thygazo)benagthadiazglehig.1 P I D -2-. roxy ie yurpe o. Dyestufi Shade of (A) Shade of (B) y aminohen lazo -benzothiadi- Fibei Fiber gfikll 1 D hoxy-4 2 -hydroxy-4 -plieny d0 o. fianethoryA-(T-hydroiy4-di Purple Puiple. 5 y ai i w w gggiglg-BgellyilZO)-b(ll'lZ0thl8-dl- 20 m 1320 5- th s '-4 (2-h dro '-5-metli 1- Blue reen Blue reen G-nmthOXy -(2'-hyd1'OXy3',5-d1- Green Green. me y E y g g l g i g phenylazo)-benzothiadiazoletiia iazo e-1 enwamXMe -i.ydwxy-s -aiim- Blue Blue. g gggrg glg512 33-3 3 Gm Greenplge'lyl-l-2lZ0)-b6l1ZOLlll3dlflZO10- thiad i zolei 2 3 Z e Z I irrietho y4 (2 -hydroay-1 -naph- Purple Purple 6 mcfliouii (2 i j tliylazo)-beiizotliiadiazole-1,2,3.

glif fg fgg "170) bemot 1m 5-n1etlioxy-fichloro-4-(2-hydroxydo Do i.z sothoxy l-(z-hydroxy-3 -tert- Green Green. ygnlpmhylam)'benzothladmmle' ggggfififl gfi gg 35 5-nietlioxy-fi-ehloro4-(2'-hydroxy- Greeriish blue... Greenish blue.

v a 4 v G-mehhOXY-l-(Z ilydlOKY-W-FIG: do Sli htly blueisli g ggfgg g benzothm g gflii g green" 5-n etlioxy fi cliloro-4-(2-liydroxy- Blue green Blue green.

fi-inetlioxy et-(T-hydroxy-5-beiizyl ..d0 Do. ifif zgggsg ffi i'fiyghenylwo) benzommdmzole' 5-rnethoxy 6-elil(iro-4-(Z-hydroxy- ..do o-nietlioxy-i-(1 liYdroxy l-;nethyl- Green blue Green blue. 40 g g g g g g g g o,7-diruethyl-l (2-hydroxy-1-naph- Purple i thylazo)-berizotliiadiazole-1 2 .5. G-methoz.y-i-(P-(o-olilorophenyl)-3- Golden eolor Golden color. v

mothyl-5-pyrazoloii4-ylazo)- 4 g g gg gg i g P mp1s benzothiad1azole-1,2,3. 6-metlioxy-4-(1'-(o-metl1ylpiienyl)- Yellow orange. Yellow orange.

3'-rnethyl-5-pyrazolon-4-ylazo)- EXAMPLE 12 Red purple Red purple.

Orange yellow- Orange yellow.

Yellow Yellow.

Green blue Green Green.

.do Do.

Slightly reddish violet.

4 grams of 4 amino S-rnethoxy-Z,1,3-benzothiazole were dissolved into a solution of 34.3 g. of 35% hydrochloric acid and 137 g. of water and the soltuion so prepared was cooled to 0 to 5 C. 1.68 grams of sodium nitrite were added thereto quickly in the form of solid, and the solution was stirred for 40 minutes at this temperature. On addition of 0.5 g. of decolorizing carbon, the solution was filtered. The so prepared red brown transparent diazotized solution was dropped at 15 C. into a coupling component solution prepared by dissolving 3.83 g. of m-diethylaininophenol into 38 g. of glacial acetic acid and stirred at this temperature for 15 minutes. Thereafter, crystalline sodium acetate was added to adjust the pH to a range between 4 and 5. After further stirring at this temperature for 2 hours, the precipitated brown purple crystals were filtered and again suspended in 200 cc. of water, followed by neutralization with 10% aqueous ainmonia to a pH of 7.5 to 8.

They were filtered, washed with water and dried at room temperature .and a reduced pressure. There were obtained 7.2 g. of brown purple crystals having a melting point of 140 to 143 C. Purple crystals having a melting point of 145 to 146 C. were obtained further 'by recrystallization from ethanol. The crystals were 4-(1'- hydroxy 5 N,N diethylarnino phenyl 2' 2120)- 5-rnethoxy-2,1,3-benzothiazole. N analysis values: calculated 19.60%, found 19.56%.

30 grams of the thus obtained dyestuff were well kneaded with 15 got a condensation product formed from 2 moles of naphthalene sulphonic acid and 1 mole 13 of formaldehyde, g. of sodium N-dodecyl-2-methylbenzoimidazole-5-sulphonate, 20 g. of sodium p-toluene sulphonate by means of three rolls. The obtained paste was dried at 60 C. and pulverised on a super high speed pulverizer to form a dyestuif composition in the form of fine particles.

0.5 gram of the dyestuff composition so obtained (30% pure content) was added to 300 cc. of water at 40 C. to form a homogeneous dispersion. g. of a filament which has been prepared by melt spinning .a chip mixture com- 14 had an excellent fastness to sunlight (Grade 6) washing (Grade 5), rubbing (Grade 5), sublimation (Grade 4) and drycleaning (Grade 5) and also a lightness of 4.4%, a purity of 4.8% and a dominant wavelength of 449.0 mg.

EXAMPLE '14 4-amino 5 methoxy 2,1,3 benzothiadiazole was diazotized in the same manner as in Example 12 and coupled with alkylphenol and alkoxynaphthol. The names prising 95 parts of powdery isotactic polypropylene hav- 10 of dyestuffs obtained, their melting points, the results of ing an inherent viscosity of 1.53 (measured in tetralin of coloring and fastness properties are tabulated below.

TABLE V Result of Dyeing Color value Fastness to- Melting Shade of poly- Shade of poly- Domi- Dyestuft point, C. propylene fiber propylene fiber Light- Purity nant containing 5% of containing 5% of ness Percent wave- Wash- Rub- Subli- Drynickel stearate zinc stearate Percent length, Light ing hing mation clean- Inp mg 4-(1-hydroxy-4-methoxy- 188-192 Grey Grey 3.9 3.9 445.0 5-6 5 5 5 5 naphthyl-2-azo)-5-Inetl1oxybenzothiadiazole. 4-(1-hydroxy-5-N,N-di- 205.5-207 Black Black 4.2 5.3 452.1 5-6 5 5 5 5 methylaminophenyl-2- azpyfi-methoxy-benzothia- 4-(l -l iydroxy-5-N-phenyl- 116-120 Grey Grey 9.4 5.3 563.0 5 5 4 4 5 aminophenyl-2-az0)5- methoxybenzothiazole.

135 C.) and 5 parts of zinc stearate at 240 C. and EXAMPLE It to times i l i m z i 4.4 grams of 4-arnino-5-methyl-2,1,3-benzothiadiazole ggi gi gg i 1S i fl i 0 were diazotized in the same manner as in Example 12 i ig ours T' H e and the obtained diazotized solution was dropped at 10 g g F soap g a to 15 C. into a coupling component solution prepared d g g d aving 3: 8 5 by dissolving 4.6 g. of 1-pheny1-3 methyl-5-pyrazolone J e edsnmg m g. 2; i into a solution of 55.5 g. of 30% caustic soda :and 183 g. i a; e 2% m g t of Water. After stirring for 30 minutes at this temperature, 1g 21 E f a Pun y o a an Omman the precipitated coloring matter was filtered. The treatengt o ment was carried out in the same manner as in Example 13 to form 7.5 g. of black brown crystals having a melt- EXAMPLE 13 ing point of 115 to 125 C. Further, dark brown crystals 4.6 grams of 4 amino 5 methOXY ,3 benzo- 40 having a melting point of 164 to 165 C. were obtained thiadiazole were dissolved in a solution of 39.4 g. of 35% by recrystallization from 70% aqueous dioxane. The hydrochloric acid in 158 g. of water and the solution was crystals were 4 (1 phenyl-3-methyl-5'-pyrazolon-4- cooled to 0 to 5 C. After quickly adding 1.93 g. of ylazo) 5 methyl 2,1,3 benzo-thiadiazole. N analysis sodium nitrite in a solid form, the solution was stirred values: calculated 22.94%, found 22.91%. for 40 minutes at this temperature. The so prepared red This dyestufl colors :a polypropylene fiber containing brown transparent diazotized solution was dropped at 5% zinc stearate in yellowish red. The dyeing had an 10 to 15 C. into a coupling component solution preexcellent fastness to sunlight (Grade 5-6), washing pared by dissolving 3.86 g. of fi-naphthol into a solution (Grade 5), rubbing (Grade 5), sublimation (Grade 5) of 55.5 g. of 30% caustic soda in 183 g. of water. After and drycleaning (Grade 5) and also a lightness of 17.0%, stirring for 30 minutes at this temperature, the precipia purity of 64.0% and a dominant wavelength of 600.5 tated coloring matter was filtered and was again susm pended in 200 cc. of Water. The suspension was then In the same manner as above, the following two dyeaoidified with a dilute hydrochloric acid to Congo red stufis were prepared from 4-amino-2,l,3-benzothiadiazole and was adjusted with 10% aqueous ammonia to a pH and two pyrazolone derivatives. The melting points, the of 7.5 to 8. It was again filtered, washed with water and results of analysis and the results of dyeing of a polydried at C. Thus, 6.9 g. of red purple crystals having propylene fiber containing 5% of nickel stearate with the a melting point of 142 to 145 C. were obtained. Further, use of the dyestuifs are shown in Table VI.

TABLE VI Results of Dyeing Melting N analysis value, Dyestufi point, percent Fastness to- 0. Color Shade Found Calculated Sunlight Washing Rubbing Subli- Dry motion cleaning 4-(1,3-di1nethyl-5-pyrazolon-4- 213-214 30.58 30. 64 Yellowish re(l 5-6 5 5 5 5 ylazo)-2,1,3-benzothiadiazole. 4-(1-ethy1-3-methyl-5-pyrazol0n- 169171 29. 09 29.15 do 5-6 5 5 5 5 4-ylazo)-2,1,3-benzothiadiazole.

red purple crystals having a melting point of 146 to 148 EXAMPLE 16 C. were obtained by recrystallization from of 70 aqueous dioxane. The crystals were 4-(2'-hydroxynapl1- thyl-1'-azo)-5-methoxy-2,1,3 benzothiadiazole. N analysis values: calculated 16.66%, found 16.63%.

This dyestulf colors :a polypropylene fiber containing 4-arnino-5-methyl-2,1,3-benzothiadiazole was diazotized in the same manner as Example 15 and coupled with the below indicated coupling components. The melting points of the obtained dyestuffs, the results of dyeing and fast- 5% of zinc stearate in slightly blueish grey. The dyeing 7 5 mass properties are tabulated below.

TABLE VII Result of Dyeing Color value Festness to- Shade of poly- Shade of poly- Domi- Couphng component propylene fiber propylene fiber Light- Purity, neut Wasr- Rub- Suhli- Dry- Melting containing 5% of containing5%of ness, Percent wave- Light ing bing mation cleanpoiut, C. nickel stearate zinc stearate Percent length, ing

Q-naphthol 193. 5-1950 Slightly 7.6 25.0 485.7 5 5 5 5 5 greenish grey. N,N-dimethy1amino-phenol 128-130 Blac' 3.2 7.0 550.5 5-6 5 5 4 5 TABLE VIII Result of Dyeing Color value Fastness to Shade of poly- Shade of poly- Domi- Dyestufi propylene fiber propylene fiber Light- Purity, nant Wash- Rub- Subli- Dry- Melting coutaining5% of containing5% of ness, Percent weve- Light ing hing motion cleanpoint, (J. nickel stearate zinc stearate Percent length, ing

4-(1-hydroxy-4-tert- 135.5-137 Dark green 5.5 16.0 499.8 5 5 5 5 5 butylpl1enyl-2'-azo)-2,1,3- benzothiadiazole. 4-(1-hydroxy-4'-Iuethoxy- 132-134 Deep green 5. 4 14. 9 498. 6 5-6 5 5 4 5 phenyl-2-azo)-2,1,3- benzothiadiazole. 4-(1'-hydroxy-5'-N,N- 176.5-l77.5 Black 3.8 6.1 557.5 5-6 5 4 5 5 diethylomino-pl1enyl-2-az0)- 2,1,3-henzothiadiazole.

EXAMPLE 17 TABLE IXContinue'l 4.5 grams of 4-am1no-2,1,3-benz0thrazole were dlS- Sh d I 1 S1 (1 I I aeo poyiaeopoysolved into a solution of 33.9 g. of 35% hydrochloricacid Dyosmfi propylene fiber propylene fiber in 135 g. of water, and cooled to O to 5 C. On addition containing containing of 1.60 g. of sodium nitrite, the solution was stirred for mckelstwate me swarm 40 minutes. After addition of 0.5 g. of a decolorizing 4-t1-hydroxyi-methoxy-2-naph- Slightly blueish Siightlyblueish carbon, the solution was filtered to obtain a diazotized solution. This diazotized solution was dropped into a coupling component solution prepared by dissolving 4.1 g. of m-dirnethyl-amino-phenol into g. of glacial acetic acid in the same manner as in Example 12. 7.0 g. of 4-(1'- hydroxy-5-N,N-dimethylarnino-phenyl 2' azo) 2,1,3- benzothiazole were recrystallized with ethanol to form a dyestufi having a melting point of 204 to 206 C. N analysis values: calculated 23.41%, found 23.27%.

This dyestutf colors a polypropylene fiber containing 5% of zinc stearate in dark black. The dyeing had an excellent fastness to sunlight (Grade 5-6), washing (Grade 5), rubbing (Grade 5), sublimation (Grade 5) and drycleaning (Grade 5) and also a lightness of 5.4%, a purity of 4.5% and a dominant wavelength of 561.7 m

Similarly, with the use of 4-amino-2,1,3-benzothiadiazole, the following dycstufis are obtained. The melting points, the results of dyeing, color values and fastness properties are tabulated in Table VIII above.

EXAMPLE 18 Monoazo dyestuffs indicated in Table IX were prepared by coupling various 4-an1ino-2,1,3-benzothiadiazole derivatives with various coupling components. A polypropylene fiber containing 5% of a metal compound is colored by each of these dyestuffs. The obtained shades are shown in Table DC phenylazo)-5-rnethoxy-henzothiadiazole-2,1,3.

4-(2 -liydroxy4 -phenyla1ninophenylazo)-5-methoxy-benzothiadiazole-2,l,3.

Slightly blueish Slightly blueish black. black.

4-(2-hydroxy-5-metl'ioxyphenyl- Green Green.

azo)-5-methoxy-benzothiadiazole- 2,1,3.

4-(2-liydroxy-4'-butylaininophenyl- Slightly blueish Slightlyblueish azo)-5-meth0xy-benzotliiadiazoleblack. black. 2,1,3.

4-(2'-hydroxy-4-N-ethyl-N-benzyl- Black Black.

uminophenyluzo)-5-niethoxybenzothiadiazolezlfi.

thylazo)-5-methoxy-benzothiadia- 4-(5'41ydroxy-5-methoxyphenylazo)-5-inethyl-benzothiacliazole- 2 grey. grey.

Blueish grey. Blueish grey.

.. .do Do.

Red Red.

Slightly blueish Slightly blueish black. black.

Dark brown Brown.

Orange yell0w Orange yellow.

Red purple... Red purple.

Orange Orange.

Dark blue Dark blue.

Black Black.

Slightly blueish lllueis'h black.

black.

do Do.

Black Block.

Slightly blueish Slightly blueish black. black.

Blackish blue--. Blaekish blue.

Green Green.

...do Do.

Blueish black. Blueish black.

Yellow orange. Yellow orange.

- do Do.

Red orange- Red orange.

Brown Brown.

Orange Orange.

Dark blue Blue.

Slightly hlueisli Blueish black.

black.

TABLE IX-Continued 4-(2hydroxy-1-naphthylazo) -6- methyl-benzotl1iadiazole-2,1,3. 4-(2-hydroxy-1-dimethylaminophenylazo)-6-methyl-benzothiadiazole-2,1,3. 4-(2-h ydroxy-l-naphth ylaz -6- rnethox y-benzothiadiazole-2,l,3. 4-(2 -hydr0xy-4 -diethylan1in0- phenylazo)-6-methoxybenzothiadiazole-2,1,3. 4-(2-hydroxy-1-napthylaz0)-7- methoxy-benzothiadiazole-2,1,3. 4-(2-hydroxy-4-dibutylaminophenylazo)-7-methoxybenzotl1iadiaz0le-2,l,3. 4-(Zhydroxy-4-diethylaininophenylazo)-5-chloro-benzothia- (Mamie-2,1,3. 4-(2-l1ydr0xy-4-dieth ylaminophenylazo)-5,7-dimetl1yl-benz0- thiadiazole-2,1,3. 4-(2-hydroxy-4-diethylaminoplienylazo)-5chloro-7-methylbenzothiadiaz0le.2,l,3. 4-(2"hydroxy-4'-diethylaminophenylazo)-5-methoxy-7-methylbenzothiadiazole-2,1,3. 4-(2-hydroxy-4diethylaminophenylazo)-5-eth0xy-7methylbenzothiadiazo1e-2,1,3. 4-(2-hydroxy4-diethylamin0- phenylaz o) -5-n1ethyl-7-metli oxybenzothiadiazole-2,l,3. 4-(2-hyclroxy-4-diethylaminophenylazo)-5,7dimethoxy-benzothiadiazole-2,1,3.

1. A water-insoluble monoazo dyestufi having the for- Shade of poly- Shade of propylene fiber polypropylene containing nickel fiberstearate containing zinc stearate Blueish blaek Do.

.... do D0.

Blue black .{Blue black.

Black Do.

Blue black Do.

Black Black.

Slightly blucish Slightly blueish black. black.

We claim:

mula

wherein is a member selected from the group consisting of substituted and unsubstituted benzothiazolyl, substituted and unsubstituted 1,2,3 benzothiadiazolyl, and substituted and unsubstituted 2,1,3-benzothiadiazolyl, the substituents being selected from the group consisting of lower alkyl, lower alkoxy, di(lower) alkylamino, Cl, Br, lower alkanoylamino and mercapto, and A being a member selected from the group consisting of phenyl, naphthyl, acenaphthyl, pyrazolonyl, thionaphthyl, cyclohexanyl, cyclohexenyl, 1,3-indandionyl, naphthindandionyl, acetoacetyl and aceto (lower)- alkyl, a hydroxyl group being attached to A at one of the positions ortho with respect to the position of attachment of said A to the -N=N- group and the other positions of said A being severally substitutable with a member selected from the group consisting of H, Cl, OH, lower alkyl, allyl, lower alkoxy, benzyloxy, lower alkylamino, benzylamino, di(lower)alkylarnino, phenylarnino, phenyl, chlorophenyl, bromophenyl, lower alkylphenyl, lower alkoxyphenyl, carboxy(lower) alkyl, CONH and morpholino.

2, 4 (1-hydroxy-5'-N,N-diethylaminophenyl-2'-azo)- 2,1,3-benzothiadiazo1e.

3. 4 (1-hydroXy-4'-methoxynaphthyl-2'-azo)-6-methoxy-2-methy1-benzothiazole.

4. 4 (1'-hydroxy-4'-tert-butylphenyl-2'-azo)-6-methoxy-1,2,3-benzothiadiaz0le.

5. 4 (l'-hydroxy-4'-rnethoxyphenyl-2'-azo) -6-methoxy- 1,2,3-benzothiadiazole.

6. 4 (1-hydroxy-5'-N,N-diethylaminophenyl-2-azo)- S-methoxy-Z,1,3-benzothiadiazole.

References Cited UNITED STATES PATENTS 1,076,249 10/ 1913 T homaschewski 260-158 2,023,773 12/1935 Schrader 260-158 2,109,552 3/ 1938 Schindhelm et a1. 260-158 FOREIGN PATENTS 1,290,839 3/ 1962 France.

' OTHER REFERENCES Kiprian-ov et 211.: CA, vol. 49, p. 892613 (1955).

FLOYD D. HIGEL, Primary Examiner. 

